This study examined the effects of bread crumb and crust structure on volatile release and aroma perception during oral processing. French baguettes with different crumb structures were procured from a supermarket or local bakeries (n = 6) or produced in the laboratory via par baking (n = 3). Eight study participants consumed crumb-only and crumb-and-crust samples, and the resulting volatile release was measured in vivo using proton transfer reaction-mass spectrometry. A statistical model was then used to examine the contributions of volatile compounds to target ion production (i.e., crumb or crust markers). Utilizing the three laboratory-produced breads, chewing behavior and aroma perception were measured via electromyography and the temporal dominance of sensations method, respectively. The results revealed that the initial levels of crumb markers as well as crumb firmness affected the crumb markers release. Crust markers were released more quickly than crumb markers, leading to different perception dynamics.